Phenyl-azo-n-acylamidoethylaniline compounds

ABSTRACT

Mono- and dis-azo compounds particularly useful for dyeing polyamide textile materials in deep yellow to red crock-fast shades with excellent fastness to light and brightness and improved buildup and contain a phenyl or phenylazophenyl diazo component and an aniline coupling component, the nitrogen atom of which is substituted with an acylamidoethyl group camera ready copy.

llnited States Patent 11 1 Weaver et a1.

1 1 Mar. 4, 1975 1 Pll-lENYL-AZO-N- ACYLAMIDOETHYILANILINE COMPOUNDS [75] Inventors: Max A. Weaver; Clarence A. Coates,

Jrn, both of Kingsport, Tenn.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

122 Filed: Oct. 29, 1971 21 Appl. No.: 194,047

[52] U.S. Cl. 260/207.l, 8/41 B, 260/187, 260/346.1 R, 260/465 E, 260/557 R, 260/561 R, 260/562 R, 260/570.5 P [51] Int. CL... C09b 29/08, C09b 31/04, D06p 3/24 [58] Field of Search 260/207.l, 207, 152, 187,

3,393,191 7/1968 Mueller 260/205 3,510,470 5/1970 Dickey et a1 260/207.l 3,535,306 10/1970 Altermatt et a1. 260/207.1 3,546,204 12/1970 Weaver et a1 260/205 3,547,571 12/1970 Angliker 260/207.1 X 3,574,183 4/1971 Kruckenberg 260/207.1

FOREIGN PATENTS OR APPLICATIONS 734,846 4/1943 Germany 260/207.1 963,457 5/1957 Germany 260/207.1 754,146 3/1967 Canada 260/158 OTHER PUBLICATIONS Altermatt et al., Chemical Abstracts, Vol. 73, p. 68, Article 89144c, (1970).

Primary Examiner-Floyd D. Higel [57] ABSTRACT Monoand dis-azo compounds particularly useful for dyeing polyamide textile materials in deep yellow to red crock-fast shades with excellent fastness to light and brightness and improved buildup and contain a phenyl or phenylazophenyl diazo component and an aniline coupling component, the nitrogen atom of which is substituted with an acylamidoethyl group camera ready copy.

8 Claims, N0 Drawings PHENYL-AZO-N-ACYLAMIDOETHYLANILINE COMPOUNDS This invention concerns certain novel azo compounds useful as dyes for synthetic textile materials such as polyamide, cellulose acetate and polyester fibers. yarns and fabrics. This invention also concerns polyamide textile materials dyed with our novel azo compounds.

The azo compounds of our invention have the general formula wherein R is hydrogen, halogen, cyano or the group -SO R in which R is one of the alkyl. aryl or cyclohexyl groups which R can represent;

R is (()R, cyano. carbamoyl. lower alkylcarbamoyl, formyl, arylazo. or SO ,R',

R" is hydrogen or halogen;

R is hydrogen. lower alkyl or the group NHCOR R is hydrogen or lower alkyl;

R" is hydrogen. alkyl of up to about eight carbon atoms. or cyclohexylmethyl; and

R is lower alkyl; lower alkyl substituted with halogen, hydroxy. lower alkoxy. cyano, carbamoyl, lower alkanoyloxy or cyclohexyl; lower alkoxy; lower haloalkoxy; cyclohexyl; aryl; 2-furyl; or morpholino;

in which each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.

Our novel compounds exhibit excellent fastness to light. brightness and dyeability on polyamide fibers and. accordingly. are especially useful for dyeing such fibers. particularly polyamide carpet fibers. The improved dyeabilitiy of our novel compounds is manifested by the deep yellow to red, crock-fast shades they produce on polyamide fibers. Our compounds also exhibit improved build-up which is another aspect of a dye compound's dyeability properties. These improved properties distinguish our novel compounds from the The substituents represented by each of R through R are well known to those skilled in the art. As used herein to describe an alkyl moiety, "lower" designates a carbon content of one to about four carbon atoms. Chlorine and bromine are preferred halogen atoms. It is also preferred that only one of R and R is an alkyl group.

A group of our novel compounds which, because of their costzperformance ratio, are especially preferred are those in which R is hydrogen, chlorine, bromine, cyano or lower alkylsulfonyl; R is lower alkylsulfonyl. cyano or lower alkoxycarbonyl; R is hydrogen, chlorir re or bromine; R is hydrogen. methyl or lower al- Ranoylamino, especially, acetamido; R 15 hydrogen; R is lower alkyl; and R is lower alkyl or lower alkoxy.

Our novel compounds are prepared by diazotizing an amine having the formula and coupling the resulting diazonium salt with a conpler of the formula according to known procedures. Alternatively, azo

compounds in which R is cyano can be prepared by the cyanide displacement reaction in which the corresponding chloroor bromo-substi'tuted azo compound is treated with a cyanide salt in the presence of a copper catalyst according to published techniques. The

amines having formula (ll) are known compounds and-.

/or can be prepared by known techniques.

The couplers offormula (III) are prepared by the following reaction sequence:

compounds disclosed in Canadian Pat. No. 754,146. Those prior art compounds, which are designed for dyeing non-nitrogenous fibers such as cellulose acetate and polyester fibers. exhibit poor properties on polyamide fibers when compared to our novel azo compounds.

In some cases other acylating agents, such as anhydrides, may be substituted for the acylating agent hav ing the formula Cl-COR The couplers of formula (Ill) in which R is hydrogen and R is ethyl set forth in Table l are prepared according to the abovedescribed technique.

Jim

3 ,t 4 Table I of cone. H 50 The solution is cooled and 10 ml. of 1:5

acid is added below 15C. 2-Chloro-4- Making methylsulfonylaniline (2.05 g.) is added, followed by R R Acylating Agent Point, C. 10 m1. of 1:5 acid, all below 5C. The diazotization re- 5 action is stirred at O-5C. for 2 hours and added to a gig; chilled solution of 2.20 g. of N-(2-acetamidoethyl)-N- cl-l C'H 'EIH,, cnl crico o 614,2 ethyl-m-toluidine in 40 ml. of 1:5 acid. Ammonium ac- :gfi 3523 etate is added to buffer the coupling mixture. After al- 4 f & f iI 7244 lowing to stand for 1 hour, the reaction mixture is CHr rl n a n 7677 10 drowned into water. The azo product is collected by filgi li I gig tration, washed with water, and dried in air. The azo CH=CHCH=CHO CO-CH=CHCH=CHO compound obtained produces scarlet shades on polya 's W 98-100 amide fibers, has excellent fastness properties, and has I I 149450 the formula zl CH=CHCH=CHO co cH=cHcH=cHo 15 NH- QH" C.;HUCOCI 89-91 CoCH,, CH. ,C,;H C.,H -,CH CO-Cl 153-155 Cl c I? com, 2

oa cn mtcocn The azo compounds set forth in the following exam- 25 The azo compounds set forth in the examples of Table ples further illustrate the compounds of the invention. 11 correspond to formula (1) and are prepared by the procedures described hereinabove. The color given for EXAMPLE 1 each of the compounds refers'to the shade it produces Sodium nitrite (0.72 g.) 15 added portlonwlse to 5 ml. on polyamlde fibers.

Table 11 Example No. R R R R R R Color 2 Cl CH SO H CH H C H C H Scarlet 3 Cl CH SO, H CH;, H C H --CH(CH Scarlet 4 Cl CH SO H CH H C H -EH==CHCH=CHO Scarlet 5 Cl CH SO H CH; H C H, OC H Scarlet 6 Cl CH SO H ---CH H --C H CH Cl Scarlet 7 Cl CH SO H CH H C H OCH CH Cl Scarlet 8 Cl CH SO H CH: H C H CH,OC H Scarlet 9 Cl CH SO H CH H C H CH C H Scarlet 10 Cl CH SO H CH H C H r, -C H Scarlet l 1 Cl CH SO H CH; H C H C H Scarlet 12 -Cl CH SO Cl -CH;, H -C H, CH; Yellow- Brown 13 Cl CH SO Br CH; H -C H CH; Yellow- Brown 14 Br CH SO Br H H C H CH; Yellow- Brown 15 --Cl CH SO H H H C H CH Orange 16 Cl CH SO, H H CH: H CH Orange 17 Cl CH SO H CH CH; H CH; Scarlet 18 Cl CH SO H NH- CH; H CH; Scarlet COCH; 1) Cl CH SO H NH- H -C,H CHa Scarlet COCH; 20 SO CH CH SO H CH H C,H -CH Red 21 CN CH;SO H CH H C H CH Red 22 SO,(CH CH;, CH SO H CH H --C H -CH Red 23 Cl CH S0 H CH; H (CH CH CH; Scarlet 24 Cl CH S0 H CH; H -CH,CH(CH -CHJ Scarlet 25 Cl CH SO H CH; H CH C H CH Scarlet 26 *Cl CH SO H -CH H CH(CH )C H -CH Scarlet 27 Cl cH so H -CH H -C,H CH,CH,OH Scarlet 28 Cl CH, SO H CH; H -C H, (CHz)aoH Scarlet 29 --Cl CH SO H CH: H H CH CN Scarlet 30 Cl CH SO H CH H CH(C Hs)(CH CH CH CONH Scarlet 31 Cl C H so H CH H -C,H CH,0H Scarlet 32 Cl CH SO H CH H C H -CH C- Scarlet H OOCCHQ 33 H CN H- CH H C,H CH; Orange 34 Cl --CN H H CgHg CH Red ide textile materials according to known disperse dyeing techniques. Various dispersing and wetting agents can be employed in the dispersion of the finely divided dye compound in an essentially aqueous dyebath. Procedures by which the compounds of the invention can be applied to polyamide textile materials are described in U.S. Pat. Nos. 3,100,134 and 3,320,021. The following example illustrates a method for applying the novel compounds to polyamide fibers.

EXAMPLE 64 The azo compound (50.0 mg.) of Example 1 is dispersed in cc. of 2-methoxyethanol. Asmall amount (3-5 cc.) of a 3% sodium lignin sulfonate solution is added, with stirring, and then the volume of the bath is brought to 150 cc. with water. A 5 g. textile fabric made of nylon 66 fibers is placed in the bath which is then slowly brought to the boil. The dyeing is carried out at the boil for one hour with occasional stirring. The dyed fabric is then removed from the dyebath, rinsed with water, and dried in an oven at 250F. The fabric is dyed a bright scarlet shade exhibiting excellent fastness properties when tested in accordance with the procedures described in the Technical Manual of the American Association of Textile Chemists and Colorists. 1968 edition.

The polyamide materials which can be dyed with the novel azo compounds are well known and include nylon 66 (polyhexamethylene adipamide) manufactured by the polymerization of adipic acid and hexa' methylenediamine, nylon 6 Polycaprolactam) prepared from epsilon-aminocaproic acid lactam (caprolactam and nylon 8. A detailed description of the synthetic polyamide materials which are dyed bright, fast shades by the compounds of the invention is set forth in U.S. Pat. No. 3,100,134.

The invention has been described in detail with parbut it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A compound having the formula R R R6 CH2CH2NHCOR7 wherein R is hydrogen, chlorine, bromine, or lower alkylsulfonyl; R is phenylazo or lower alkylsulfonyl; R is hydrogen, chlorine or bromine; R is hydrogen, lower alkyl or the group NHCOR R is hydrogen or lower alkyl; R is hydrogen, alkyl of up to about eight carbon atoms or cyclohexylmethyl; and R is lower alkyl; lower alkyl substituted with chlorine, hydroxy, lower alkoxy, cyano, carbamoyl, lower alkanoyloxy or cyclohexiyl; lower alkoxy; cyclohexyl; phenyl; phenyl substituted with lower a1- kyl, lower alkoxy or chlorine; or 2-furyl. 2. A compound according to claim 1 wherein R is hdyrogen, chlorine, bromine, cyano or lower alkylsulfonyl; R is lower alkylsulfonyl, cyano or lower alkoxycarbonyl; R is hydrogen. chlorine or bromine; R is hydrogen, methyl or lower alkanoylamino; R is hydrogen; R is lower alkyl; and R is lower alkyl or lower alkoxy. 3. A compound according to claim 1 having the formula cnsso Nca cfi lmcocn 4. A compound according to claim 1 having the for mula cn so NHCH CH NHCOCH 6. A compound according to claim 1 having the form u la i ao -NCHsaCHzNHCOCHa 7. A compound according to claim 1 having the formula v NCHZCHQNHCOCHB 8. a compound according to claim 1 having the formula PO-1050 UNITED STATES PATENT OFFICE (5/69) CERTIFICATE O CORRECTION PetentNo. 3,869,442 Dated March 4,1975

Inventods) Max A. Weaver, Clarenee A. Coates, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Line 8 of the Abstract delete "camera r'eady copy" and insert Column 8, line 5, the formula in Claim 6 should read Signed and Seal-ed this twenty-fifth Day Of November 1975 sun v Arrest:

. R'UTHIC. MASON c. MARSHALL DANN L Allesling Office Commissioner ul'PaIenIs and Trademarks J 

1. A COMPOUND IF THE FORMULA
 2. A compound according to claim 1 wherein R1 is hdyrogen, chlorine, bromine, cyano or lower alkylsulfonyl; R2 is lower alkylsulfonyl, cyano or lower alkoxycarbonyl; R3 is hydrogen, chlorine or bromine; R4 is hydrogen, methyl or lower alkanoylamino; R5 is hydrogen; R6 is lower alkyl; and R7 is lower alkyl or lower alkoxy.
 3. A compound according to claim 1 having the formula
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 1 having the formula
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 1 having the formula
 8. a compound according to claim 1 having the formula 